Method of preparing rubber compositions having improved physical properties



3,325,429 METHGD F PREPARING RUBBER COMPOSI- TIONS HAVING IMPROVED PHYSICAL PROPERTIES James Donald Harris, 6 Marlborough Close, Macclesfield, England No Drawing. Filed May 31, 1966, Ser. No. 553,713 13 Claims. (Cl. 26023.7)

This application is a continuation-in-part of my copending applications Ser. No. 207,084, filed July 2, 1962, now abandoned, and Ser. No. 274,781, filed Apr. 22, 1963, now abandoned.

This invention relates to rubber compounds and methods of compounding rubber for the purpose of obtaining improved physical properties. It is applicable to natural rubber, and to polyisoprene, polybutadiene, styrene-butadiene, oil extended styrene-butadiene and nitrile rubbers.

According to the invention, rubber is compounded with a reinforcing filler comprising finely divided silicas or silicates, the composition is subjected to heat treatment, and a metallo-origanic compound as defined below is added to the heat treated composition.

The metal organic compounds used according to the invention comprise products of reaction between aluminum alkoxides or polyoxo aluminum alkoxides and carboxylic acids, namely polyoxo aluminum stearate, polyoxoaluminurn tallate and polyoxo aluminum benzoate.

The metallo-organic compounds further include compounds obtained by condensing alkoxides or aryloxides of trivalent elements with acyloxides of divalent metals or radicals, and compounds obtained by reacting certain metal oxides, e.g. litharge, with polyoxo aluminum acylates. The trivalent elements include especially aluminum and boron, and the alkoxides may be derived from a volatile alcohol such as isopropanol or s-butanol, or the alkoxides or aryloxides may be used in the form of condensed compounds such as polyoxo aluminum alkoxides or aryloxides. The divalent metals and radicals include zinc, calcium, strontium, barium, beryllium, magnesium, cadmium and the zirconyl radical. The acid radicals may be those of one or more carboxylic acids and sulphonic acids, including acetic acid, propionic acid, methacry-lic acid, tall oil and tall oil fatty acids, naphthenic acids, synthetic carboxylic acids in the range C C maleic acid, phthalic acid, sebacic acid, azelaic acid and dimerised fatty acids.

Whereas rubber compounds containing finely divided silicas alone as reinforcing fillers are inferior to those containing carbon black in respect of abrasion resistance, modulus, flex resistance and compression set, compounds made according to this invention using silicas have given abrasion resistance, modulus and compression set similar to those obtained with carbon black, together with superior resilience.

The silica, or aluminum, calcium or magnesium silicates may be used in the usual quantities such as 50 parts by weight per hundred parts of rubber.

The metallo-or-ganic compounds may be derived from aliphatic or aromatic acids, and may be used in quantities of 1-20 parts, preferably 3-8 parts, per hundred parts of rubber.

The silica or silicate, may be incorporated with the rubber by means of a mill or internal mixer. The metalloorganic compound is added after heat treatment. Other processing ingredients are added after heat treatment, apart from the antioxidant which is added previously.

The heat treatment may be carried out at temperatures of IOU-200 C., preferably l40-l80 C., for periods of from 3 minutes at the higher temperatures to 30 minutes at the lower temperatures.

nited States Patent 6 "ice The invention is illustrated by the following examples:

EXAMPLE 1 A compound according to the invention was prepared as follows:

Parts by wt. Natural rubber 100 Finely divided silica 50 Zinc oxide 5 Stearic acid 3 MBTS 1 DPG 2 Antioxidant 1.5

Sulphur 2.5 Metallo-organic compound 3 (1) A master batch of natural rubber, silica and antioxidant was mixed in an internal mixer. The initial temperature of rotors and case was 50 C., total mixing time was 8 minutes and final temperature was 165 C. The other compounding ingredients were added to this masterbatch on a two roll mill at 60 C.

(2) As 1, but 3 parts, of zinc aluminum tallate was added on the mill at 60 0., followed by the other compounding ingredients.

(3) A compound was mixed entirely on the mill at a temperature of 60-70 C., to the formulation given. The compound was mixed in one operation and zinc aluminum tallate was incorporated.

These three compounds were cured and tested and the following properties obtained. Vulcanisates were cured at 141 C.

Results:

l 1 i 2 l 3 Mooney plasticity at 100 C 70 33 9t Mooney scorchtime at 120 C. (nuns). 18 23 3t Tensile strength (p.s.i.).. 3, 800 4,140 4, 02( Modulus at 300% (p.s.i.)..... l, 100 1, 480 Percent elongation at break. 650 600 675 Tear strength (p.s.i.) 2,100 2,250 2, ()St Hardness (B.S. degrees) 70 7t Abrasion resistance index. 65 Percent resilience 64 74 52 Percent; compression set. 10. 4 7. 0 14. 1 Flex resistance (kilocycles) 170 200 3.

EXAMPLE 2 Natural rubber/aluminum silicate Formulation: Parts by wt. Natural rubber 10C Aluminum silicate 60 Zinc oxide 5 Stearic acid 3 MBTS 0.5 DPG l.C

Antioxidant 1.5

Sulphur 2.5 Zinc aluminum tallate 3 A masterbatch of the filler and antioxidant in the rubber was prepared in the internal mixer, .to the following schedule, starting temperature 75 C., rotor speed rpm.

Time (minutes) Add premasticated rubber 0 Add first half of fillcr-l-antioxidant /2 Add second half of filler 1 /2 Heat treatment to 6 Final temperature 174 C.

The remainder of the compounding ingredients includ ing the zinc aluminum tallate were added on the mill at 60 C.

3 This compound A and a second compound B, mixed atirely on the mill and without metal-organic compound, 'ere tested, vulcanising temperature being 141 C.

Results:

[ooney plasticity at 120 C. (ML4) 23 56 iooney scorch time at 120 0. (mins.) 23 146 ensile strength (p.s.i.).. 3,180 3,120 [odulus at 300% (p.s.i.) 1, 680 1,320 ercent elongation at break 500 525 car strength (p.s.i.) 1, 400 1,400 ardness (13.8. degrees) 69 78 u Pout abrasion resistance index 80 57 areent resilience 72 65. 5 zrcent compression set 6. 9 9. 6

EXAMPLE 3 S tyrene-butadiene rabber/ fine particle silica ormulation: Parts by wt. Styrenebutadiene rubber (Intol 1502) 100 Finely divided silica 50 Zinc oxide 3 Stearic acid 1 MBT 0.5

MBTS 0.5

DPG 2 Cumarone indene resin 3 Antioxidant 1.5 Sulphur 2.25 Metal-organic compound 3 Five metal-organic compounds were tested, respectively 00 aluminum tallate, magnesium aluminum tallate, calw,, nimum 10W 4 EXAMPLE 4 Oil extended natural rubber/ fine particle silica Formulation: Parts by wt.

Natural rubber 80 Naphthenic oil Fine particle silica 55 Zinc oxide 5 Stearic acid 3 MBTS 1 DPG 2 Antioxidant 1.5

Sulphur 2.5

Zinc aluminum tallate 3 A masterbatch of the filler and antioxidant in rubber was prepared in the internal mixer, starting temperature 75 C., rotor speed 55 r.p.m.

Schedule: Time (mins.) Add unmasticated rubber 0 Add first half of filler-l-antioxidant 1 Add second half of filler 2 Heat treatment to 9 Final temperature 175 C.

The rest of the compounding ingredients were added on the mill at 60 C.

This compound, A, and a second compound, B, containing no zinc aluminum tallate and mixed entirely on the mill were tested, vulcanising temperature 141 C.

Results:

um zinc aluminum tallate, zinc aluminum naphthenate A 1d zinc aluminum tallate methacrylate. B

Masterbatches of the filler and antloxidantln the poly- Mooney pmsmity C. (MM) 19 er were prepared in the internal mlxer, startmg temperaoomlgy stcorohltiine at)120 0. (mins)... 21. 6 39 e ensi e s rengt1 p.s.i .1 3,1"0 3,050 re 75 Ca rotor Speed 55 iuo'duh is it 300; 01. 1,430 520 ercen e onga ion a rea 1 550 750. 1 4 5381311 Tlme -2) 40 gr m stren(g}t3l1S(p(is.i.). 1, ago 1, 050 I a1 ness egrees 79 Add first half of filler+antioxidant 1 12 3:5 jfffij' fi 22 Add Second half f fill r 2 5 Percent compression set 5.1 19.3 Heat treatment to 10 Final temperature 180 C. The remainder of the compounding ingredients includ- EXAMPLE 5 g the metal-organic compounds were added to the masrbatches on the min at C Polylsoprene/ fine particle szlzca Five compounds containing the various metal organic Formulation: Parts by wt. impounds were prepared A-E) and also, a compound 50 Polyisoprene (Carifiex IR.305 ex Shell Chemical mixed entirely on the mill and w1thout metal organic Co. ltd.) 100 )IllpOUIld. Vulcanising temperature was again 141 C. Fine particle silica 50 A B C D E F ooney plasticity at 120 C. (ML4) 52 51 57 57 52 120 ooney scorch time at 120 0. (mins.). 12.0 15. 7 18 13. 4 14. 5 14 -.nsilest1e11gth(p.s.i.) 3,160 2,990 2,980 3,240 3,050 3,220 odulus at 300% .s.i.) 1,100 1,050 910 1,000 070 1,040 reent elongation at break... 550 550 575 550 550 600 tar strength (p.s.i.) 990 900 1,120 1, 110 1,040 1,100 trdness (13.5. deg1*ees) 1 69 71 71 68 68 81 1 Font abrasion resistance ndex 112 114 108 114 110 66 reent resilience 62 57 60 6O 63 48 went compression set 8. 6 5. 4 5. 4 0. 2 8. 2 21 The metal organic compounds used were: Zinc oxide -1 5 (A) Zinc aluminum tallate. Stearic acid 3 (B) Magnesium aluminum tallate. MBTS 1 (C) Calcium zinc aluminum tallate. DPG 2 (D) Zinc aluminum naphthenate. Antioxidant 1.5 (E) Zinc aluminum tallate methacryl-ate. Sulphur 2 5 (F) N11. Zinc aluminum tallate 3 A masterbatch of the filler and antioxidant in the polymer was prepared in the internal mixer, starting temperature 50 C., rotor speed 55 r.p.m.

Final temperature was 165 C.

The remainder of the compounding ingredients, were added on the mill at 60 C.

This compound A and another compound B, mixed entirely on the mill and containing no metal organic compound, were tested, vulcanising temperature being 141 C.

Results:

Mooney plasticity at 120 C. (ML4) 28 62 Mooney scorch time at 120 (mins 45 38 Tensile strength (p.s.i.) 3, 420 2, 900 Modulus at 300% (p.s.i.). 750 430 Percent elongation at break 800 825 'Iear strength (p.s.i.) l, 520 920 Hardness (13.8. degrees) 63 74 Du Pont abrasion resistance index 74 60 Percent resilience 73 52 Percent compression set 6. 3 11. 7

EXAMPLE 6 Polybutadiene/ natural rubber blend/ fine particle silica Formulation: Parts by wt. Natural rubber 50 Polybutadiene (Diene 35) 50 Fine particle silica 50 Zinc oxide Stearic acid 3 MBTS 1 DPG 3 Antioxidant 1.5 Sulphur 2 Zinc aluminum tallate 3 A masterbatch of the filler and antioxidant in the polymers was prepared in the internal mixer, starting temperature 50 C.

Schedule: Time (mins.) Add premasticated natural rubber 0 Add polybutadiene V2 Add first half of filler+antioxidant 2 Add second half of filler and circulate steam at 115 C. 6 /2 Heat treatment to 11 Final temperature 180 C.

The accelerators, Zinc oxide, stearic acid and zinc aluminumtallate were added to the masterbatch at a second stage in the internal mixer and the sulphur was added on the mill.

This compound A and another compound B, prepared on the mill at 8590 C. and containing no metal-organic compound were tested, vulcanizing temperature 141 C.

6 EXAMPLE 7 Butadiene-acrylonitrile rubber/ fine particle silica A masterbatch of the filler and antioxidant in the polymer was prepared in the internal mixer, starting temperature 50 C., rotor speed 55 rpm.

Schedule: Time (mins.) Add polymer 0 Add first half of filler-l-antioxidant 1 Add second half of filler 2 /2 Heat treatment to 10 Final temperature 185 C.

The accelerators, zinc oxide, stearic acid and magnesium aluminum tallate, were added to the masterbatch at a second stage in the internal mixer and the sulphur was added on the mill.

This compound A and another compound, B, prepared in the internal mixer in one stage and containing no metal-organic compound were tested, vulcanizing temperature 141 C.

Results:

Tensile strength (p.s.i.) 3,050 3, 030 Modulus at 300% (p.s.i.) 1, 620 1,160 Percent elongation at break 475 600 Tear strength (p.s.i.) 1,180 1, 500 Hardness (BS degrees) 87 Du Pont abrasion resistance index 118 96 Percent resilience 45 40 Percent compression set 14. 0 16. 2

EXAMPLE 8 Fine particle silica/natural rubber Formulation: Parts by weight Natural rubber 100 Finely divided silica 50 Zinc oxide 5 Stearic acid 3 MBTS 1 DPG 1 2 Antioxidant 1.5 Sulphur 2.5

1 2.25 for compositions mixed in the mill.

Time (mins.) Add premasticated rubber 0 Add first half of filler-l-antioxidant 1 Add second half of. filler 2.5 Heat treatment to 8 Final temperature was C.

8 No metal organic compound was added and the other EXAMPLE mpounding ingredients were added on the mill at 60 C. (4) As for 3, but 5 parts of a 70% solution of polyoxo Styrene butadzene rubber/fine par tzcle szlzca lminum stearate in mineral oil was added on the mill Formulation: Parts by wt. gether with the other compounding ingredients. 5 S yr ne utadi n r r l 150 100 These specimens and a specimen 5, not heat treated Finely divided silica 50 (1 without added metal organic compound, were tested Zinc oxide 3 d the following properties determined. Vulcanisates SteariC acid 1 :re cured at 141 C. MBTS 1.5

l 1 l 2 l 3 l 4 l 5 oney plasticity at 100 0. (ML4) 34 27 05 35 so toney scorch time at 120 C. (mi11s.) 17 18 16 21 nsile strength (p.s.i.) 3, 950 3, 870 4, 100 4, 150 3, 820 rdulus at 300% (p.s.i.) 1, 440 1, 500 l, 100 1, 410 800 rcent elongation at break. 600 575 575 550 675 or strength (p.s.i.) 2, 200 2, 020 2, 200 2, 100 2,050 trdness (13.8. degrees) 65 70 i 65 1 Font abrasion resistance index 1 90 92 70 100 60 rcent resilience at 20 C (Dunlop T iometer) 71 70 03 75 57 :rcent compression set 7, 4 7. 4 S. 7 7 14. 3

JComp-ared with a standard compound containing channel black, the index 01 which is EXAMPLE 9 Natural rubber/aluminum silicate DPQ 2.5 ormulation: Parts by wt. g gf Natural rubber 100 I T '2 Alumi um silicate 5O e a 'Orgamc compolfm '"fi"? 5 Zinc oxide 5 Two metal organic compounds were compared, respec- Stearic acid 3 tively 70% solutions of polyoxo aluminum stearate and MBTS 0.5 polyoxo aluminum talla-te in mineral oil. DPG 1.0 Masterbatches of polymer, filler and antioxidant in the Antioxidant 1.5 40 proportions as given were prepared in the internal mixer, Sulphur 2.5 using the following schedule, with a starting temperature 70% soln. polyoxo aluminum stearate in minf 50 C BT31 5 Time (mins.) A master-batch of the filler and antioxidant in the rubber Add Premastlcawd p y f 0 vas prepared in an internal mixer to the following sched- Add s a f fi le +antloxidant 1 .le; starting temperature 70 C.

Time (mins.)

kdd premasticated rubber idd first half of filler+ antioxidant 1 \dd second half of filler and circulate steam at {eat treatment to 8 inal temperature was 155 C.

Fhe remainder of the ingredients including the metal organic compound, were added to the masterbatch on the nill at 60 C.

This compound, A, and a second compound, B, mixed :ntirely on the mill and Without metal organic compound, were tested, vulcanizing temperature being 141 C.

Add rest of filler and circulate steam at a temperature of 115 C. 2.5 Heat treatment to 10 Final temperature was 175 C.

A B C Mooney plasticity at C. (ML4) 50 48 Mooney scorch time at 0. (mins.) 54 50 21 Tensile strength (p.s.i.) 2, 860 2, 600 2, 550 Modulus at 300% (p.s.i.) 1, 400 1, 340 850 Percent elongation at b! 450 450 525 Tear strength (psi) 790 670 880 Hardness (13.8. degrees) 65 66 84 Du Pont abrasion resistance index... 109 108 66 Percent resilience 62 62 44 Percent compression set 8.0 7. 6 25. 6

9 EXAMPLE 11 Polyisoprene/ fine particle silica A masterbatch of the filler and antioxidant in polymer was prepared in an internal mixer to the following schedule; starting temperature 50 C.

70% solution poly-0x0 aluminum stearate Time (mius) Add premasticated polymer 0 Add first half of fillers-antioxidant 1 Add remainder of filler and circulate steam at a tem' perature of 115 C. 2.5 Heat treatment to Final temperature was 165 C.

The rest of the ingredients including the metal organic compound were added to the masterbatch on the mill at 60 C. to make compound A. A second compound, B, was mixed entirely on the mill to the same formulation, but without metal organic compound and the results are given below; vulcanisates were cured at 141 C.

Tensile strength (p.s.i.) 3, 420 2, 900 Modulus at 300% (13.51.)... 750 430 Percent elongation at break 800 825 Tear strength (p.s.i.). 1, 500 920 Hardness (B.S. degrees) 63 74 Du lont abrasion resistance index 80 60 Percent resilience 73 52 Percent compression set 6. 3 11. 7

EXAMPLE 12 Polybutadicne/ natural rubber blcnd/ fine particle silica Formulation: Parts by wt. Natural rubber 50 Polybutadiene (Diene 35) 50 Fine silica 50 Zinc oxide 5 Stearic acid 3 MBTS 1 DPG 3 Antioxidant a. 1.5 Sulphur 2 70% soln. polyoxo aluminum stearate in mineral oil 5 A masterbatch of the filler and antioxidant in the polymers was prepared in the internal mixer to the following schedule, starting temperature 50 C.

Time (mins) Add premasticated natural rubber 0 Add polybutadiene /2 Add first half of filler+antioxidant 2 Add second half of filler and circulate steam at a temperature of 115 C. 3.5 Heat treatment to 11 Final temperature was 182 C.

metal organic compound. Both compounds were tested and results are given below; the vulcanisates were cured at 141 C.

Mooney plasticity at C. (ML t) 60 135 Mooney scorch time at 120 C. (mins.) (3. 9 10 Tensile strength (p.s.i.) r 2, 200 2, 280 Modulus at 300% (p.s.1'.) t 890 560 Percent elongation at break 500 650 Tear strength (p.s.i.) 880 1,020 Hardness (13.8. degrees) G2 81 Du Pout abrasion resistance ud 123 79 Percent resilience 75 54 Percent compression set 5. 0 17. 4

Two metal organic compounds were compared, respectively polyoxo aluminum benzoate and a 70% solution of polyoxo aluminum stearate in mineral oil. Masterbatches of the filler and antioxidant in the polymer were prepared in the internal mixer to the following schedule starting temperature 50 C.

(Time mins.)

Add premasticated polymer Add first half of filler+antioxidant 1 Add rest of filler and circulate steam at C. 2.5

Heat treatment to 1( Final temperature was 190 C.

The accelerators, zinc oxide, stearic acid and metal or ganic compound were added to the masterbach at the second stage in the internal mixer and the sulphur wa: added on the mill.

Compound A contained 5 rp.p.h. of the 70% solutioi of polyoxo aluminum stearate in oil, While compound I contained 3 p.p.h. of polyoxo aluminum benzoate. ThfiSt two compounds were compared with a third compount C which was mixed entirely on the mill to the same for mulation but without metal organic compound.

The results are given below. The vulcanisates wen cured at 153 C.

A B C Mooney plasticity at C. (MIA). 66 85 14 Mooney scorch time at 1 0 C (ruins 50 47 9 Tensile strength (p.s.i.) 3, 300 3, 490 3, 0E Modulus at 300% (p.s.i.) 1, 410 1, 050 9t Percent elongation at break. 475 500 57 Tear strength (p.s.i.) t 1...... 1,010 1, 020 1, 07 Hardness (13.5. degrees) 78 80 E Du Pont abrasion resistance index." 200 210 1( Percent resilience 38 38 t Percent compression sct 15. 6 17. 3 19.

In all examples an improvement in abrasion resistance modulus at 300%, resilience and compression set wa obtained by the use of this process. The process also gav much improved plasticity and resultant improved moul flow was noted.

In each of the examples, the antioxidant used was 2,0 methyl cyc1ohexyl-4,6-dimethy1 phenol, but it will b understood that any other suitable antioxidant may b used.

The silica used in the examples was a precipitated type, Ianosil VN3 and the aluminum silicate was Manosil .S9.

What is claimed is:

1. A method of preparing rubber compositions comrising compounding approximately 1 parts by weight f rubber selected from the group consisting of natural lbber, polyisoprene, polybutadiene, styrene-butadiene ibber and nitrile rubber, and mixtures thereof with an ltioxidant and with approximately 50 parts by weight E a siliceous filler, subjecting the compounded rubber I heat treatment of between 100220 C. for a period of to 30 minutes, then adding 1-20 parts by weight of an rgano metal compound selected from the group consting of-polyoxo aluminum stearate, polyoxo aluminum llate, polyoxo aluminum benzoate and organo metal )mpounds containing aluminum, at least one metal sected from the group consisting of zinc, calcium and .agnesium, and at least one acid radical derived from an :id selected from the group consisting of tall oil fatty Lids, naphthenic acid and methacrylic acid.

2. A method as claimed in claim 1, in which the metal- -organic compounds are used in quantities of 1-10 parts weight, per hundred parts of rubber.

3. A method as claimed in claim 1, in which the metal- -organic compounds are used in quantities of 35 parts 1 weight per hundred parts of rubber.

4. A method as claimed in claim 1, in which the heat eatment is carried out at temperatures of 100200 C., r periods of from 7 minutes at the higher temperatures 30 minutes at the lower temperatures.

5. A method as claimed in claim 4, in which the heat :atment is carried out at temperatures of 140-180 C.

6. A method as claimed in claim 1, in which the rubber incorporated with the filler and antioxidant and heat :atment is carried out in a rubber processing machine, ter which the metal organic compound and other inedients are mechanically incorporated.

7. The method of claim 1 wherein the addition of the gano metal compound to the heat treated rubber is rr.ied out while maintaining said rubber at a temperare of approximately 60 C.

8. A method of preparing rubber compositions, in 1ich approximately 100 parts by weight of rubber se- :ted from the group consisting of natural rubber, poly- )prene, polybutadiene, styrene-butadiene rubber, nitrile bber and mixtures thereof is compounded with an antiiidant and with approximately 50 parts by weight of finely divided reinforcing silicaceous filler, the composition is subjected to heat-treatment, and there is added to the heat-treated composition 1 to 20 parts by weight of a metallo-organic compound containing aluminum, at least one metal selected from the group consisting of zinc, calcium and magnesium, and at least one acid radical derived from an acid selected from the group consist- .ing of tall oil fatty acids, naphthenic acid and methacrylic acid.

9. A method as claimed in claim 8, in which the metallo-or-ganic compounds are used in quantities of 1-10 parts by weight per hundred parts of rubber.

10. A method as claimed in claim 8, in which the metallo-organic compounds are used in quantities of 35 parts by Weight per hundred parts of rubber.

11. A method as claimed in claim 8, in which the heat treatment is carried out at temperatures of 200 C., for periods of from 7 minutes at the higher temperatures to 30 minutes at the lower temperatures.

12. A method as claimed in claim 11 in which the heat treatment ,is carried out at temperatures of C.

13. A method as claimed in claim 8, in which the rubber is incorporated with the filler and antioxidant and heat treatment is carried out in a rubber processing machine, after which the metal organic compound and other ingredients are mechanically incorporated.

References Cited OTHER REFERENCES Gessler et al.: The Reinforcement of Butyl and Other Synthetic Rubbers with Silica Pigments, Rubber Age, October 1955 (p. 73-76).

Rinse: Aluminum Tallate Polymers, reprint from American Paint Journal, May 4, 1959.

DONALD E. CZAJA, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

R. W. GRIFFIN, Assistant Examiner. 

1. A METHOD OF PREPARING RUBBER COMPOSITIONS COMPRISING COMPOUNDING APPROXIMATELY 100 PARTS BY WEIGHT OF RUBBER SELECTED FROM THE GROUP CONSISTING OF NATURAL RUBBER, POLYISOPRENE, POLYBUTADIENE, STYRENE-BUTADIENE RUBBER AND NITRILE RUBBER, AND MIXTURES THEREOF WITH AN ANTIOXIDANT AND WITH APPROXIMATELY 50 PARTS BY WEIGHT OF A SILICEOUS FILLER, SUBJECTING THE COMPOUNDED RUBBER TO HEAT TREATMENT OF BETWEEN 100-220*C. FOR A PERIOD OF 3 TO 30 MINUTES, THEN ADDING 1-20 PARTS BY WEIGHT OF AN ORGANO METAL COMPOUND SELECTED FROM THE GRUP CONSISTING OF POLYOXO ALUMINUM STEARATE, POLYOXO ALUMINUM TALLATE, POLYOXO ALUMINUM BENZOATE AND ORGANO METAL COMPOUNDS CONTAINING ALUMINUM, AT LEAST ONE METAL SELECTED FROM THE GROUP CONSISTING OF ZINC, CALCIUM AND MAGNESIUM, AND AT LEAST ONE ACID RADICAL DERIVED FROM AN ACID SELECTED FROM THE GROUP CONSISTING OF TALL OIL FATTY ACIDS, NAPHTHENIC ACID AND METHACRYLIC ACID. 